CN104532549B - A kind of method based on Microwave Induced Plasma quick obtaining carbon/coaxial fiber of carborundum and application - Google Patents
A kind of method based on Microwave Induced Plasma quick obtaining carbon/coaxial fiber of carborundum and application Download PDFInfo
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Abstract
The invention discloses a kind of coaxial fiber of carbon/carborundum, form mixture after the steps include: to be sufficiently mixed carbon fiber, silica flour, silicon dioxide powder, be placed under vacuum or noble gas normal pressure protective condition；Utilize microwave that mixture is heated, make carbon fiber surface activate and excite pyroreaction, obtaining the coaxial fiber of carbon/carborundum.This preparation method is simple and convenient, rapidly and efficiently obtain the coaxial fiber of C/SiC that structure is preferable, antioxygenic property is superior.Product free from admixture uniform, pure and form are controlled.Additionally, due to use Microwave Induced Plasma irradiation technique, there is firing rate fast, homogeneous heating, the advantages such as thermal inertia is little, with short production cycle, reduce further preparation cost.
Description
Technical field
The present invention relates to the fast synthesis method field of a kind of coaxial fiber, be specifically related to one and lure based on microwave
Lead method and the application of the coaxial fiber of plasma quick obtaining carbon/carborundum (C/SiC).
Background technology
Carbon fiber is the Typical Representative of reinforcement in advanced composite material, in view of the high-temperature hot physical property of its excellence
Matter, the peculiar property that intensity improves in particular with the raising of usage temperature so that its Aero-Space,
The application of the high-tech sectors such as nuclear industry has the status of irreplaceability.But carbon fiber is at high temperature oxidative atmosphere
Under, it is easy to deterioration failure, become the fatal restriction of puzzlement carbon-fiber high-temperature application.For improve carbon fiber and
It strengthens the high-temperature oxidation resistant application performance of composite, and people must develop surface protection, matrix changes
The various methods such as property, to overcome or alleviated by the high-temperature oxydation of carbon fiber.
Carborundum (SiC) is important thermal structure and function ceramics, has the good compatibility with carbon fiber,
And the oxidation product silicon oxide under its high temperature is readily formed continuous print glass phase, to the diffusion of oxidizing atmosphere,
Infiltration has good restriction effect, thus protects carbon fiber core or composite.Therefore, at carbon fiber
Surface forms carborundum (SiC) protective layer, prepares and applies the coaxial fiber of carbon/carborundum (C/SiC), causing
The broad interest of people.So far, people successively develop multiple method, achieve carbonization at carbon fiber surface
The cladding of silicon protective layer, has acquired the coaxial fiber of carbon/carborundum (C/SiC).Such as Korea S Changwon
(Kim J W, Lee S S, Jung Y G, the et al.Synthesis such as the Jae-Won Kim of national university
of SiC microtube with villus-like morphology and SiC fiber[J].Journal of Materials
Reseauch, 2005,20 (2): 409-416.), during gas-solid (VS) mechanism synthesis SiC micron tube,
Achieve the acquisition of C/SiC Coaxial Nanofibers, the oxidation initial temperature of carbon fiber is carried from less than 500 DEG C
Up to about 600 DEG C.But the C/SiC Coaxial Nanofibers that this method obtains, SiC protection shell is fine with carbon
The interface cohesion of dimension core body is bad, it is difficult to realize the defense-in-depth under high temperature.
China has also carried out a lot of work in terms of the surface protection of carbon fiber, such as Beijing Aviation investigation of materials
Institute, Aerospace Material & Technology Inst., the National University of Defense technology, Hunan University, Shandong University, Chinese science
Many the units such as institute's metal institute have all carried out positive research and application work.But same in practical application
Time, there is also some shortcomings.Such as relatively conventional polymer impregnated pyrolysis method (PIP), it is necessary to first with
Expensive Polycarbosilane (PCS) resin-coating carbon fiber surface, then carry out high temperature pyrolysis, gathering outer layer
Carbon silane (PCS) resin is converted into carborundum (SiC) protective layer.This method component in pyrolytic process is damaged
Lose so that SiC shell is inevitably generated more hole；And the difference of hot expansion property, also can
Cause combining between SiC shell and carbon fiber core bad, even peel off and deteriorate protected effect further.
Chemically based vapour deposition (CVD) technology is to prepare the common method of thin film or coating, can acquire
The coaxial fiber of the finest and close carbon/carborundum (C/SiC).But it is long that method exists the response time, technological requirement is high
Deng restriction.Although some methods improved contribute to improving structure and the application characteristic of (C/SiC) coaxial fiber,
But the deficiencies such as process complexity is tediously long still make said method be subject to many limitations in terms of Promotion practice.Such as northwest
The Li Hejun of polytechnical university (Hejun Li, Haibo Ouyang, LehuaQi, Yulei Zhang, Zhengjia Li,
Jianfeng Wei.Effect of Temperature on the Synthesis of SiC Coating on Carbon
Fibers by the Reaction of SiO with the Deposited Pyrolytic Carbon Layer, J.Mater.
Sci.Technol., 2010,26 (3), 211-216.) etc. chopped polyacrylonitrile (PAN) base carbon fibre surface realize
The coating cladding of SiC, the coaxial fiber of carbon/carborundum (C/SiC) of acquiring, is improving carbon fiber
Anti-oxidation characteristics achieves ideal result.But this process is complicated, based on waiting thermal chemical vapor infiltration
On the basis of deposition 1h pyrolytic carbon, it is necessary to successive reaction 1h under 1400～1600 DEG C of high temperature, to setting
Standby also have certain dependency.
Additionally, the Sun Liangkui of the National University of Defense technology etc. (Sun Liangkui, Cheng Haifeng, Chu Zengyong, Zhou Yongjiang, Sun Guoliang,
C/SiO2The preparation of coaxial composite fibre and performance study, Journal of Inorganic Materials, 02 phase in 2009), with
SiO2Colloidal sol is shell, and polyacrylonitrile (PAN) solution is sandwich layer, uses coaxial electrostatic spinning method to be prepared for
PAN/SiO2Coaxial fiber.Then to PAN/SiO2Coaxial fiber carries out follow-up pre-oxidation, carbonization etc.
Reason, i.e. can get the C/SiO of diameter 1 μm2Coaxial fiber (has the SiO of thickness about 20nm on carbon fiber2
Coating).But the top layer of this coaxial fiber is silicon dioxide (SiO2), changing of its carbon-fiber high-temperature antioxygenic property
Property effect, hence it is evident that not as SiC protect shell；And the carbon fiber diameter of the method is meticulous, can be only applied to inhale
The fields such as ripple.Therefore, continue explore and optimize simple and effective preparation method, quick obtaining densification continuously
The coaxial fiber of carbon/carborundum (C/SiC), with improve carbon fiber application reliability under high-temperature oxidation environment and
Durability etc., remain very important practice demand.
Summary of the invention
The technical problem to be solved, based on Microwave Induced Plasma treatment technology, it is provided that a kind of
Simply, efficiently, low cost, be easy to the method that the coaxial fiber of C/SiC is the most quickly prepared in industrialization.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is: a kind of based on microwave induced etc.
The method of the coaxial fiber of gas ions quick obtaining carbon/carborundum (C/SiC), the steps include:
1) raw material mixing: by commercially available carbon fiber, silica flour, silicon dioxide powder mix homogeneously, and add pottery
In porcelain crucible；
Described carbon is 2～5:1 with the mol ratio of element silicon；Described silicon and silicon oxide mol ratio are 0.5～2:
1；
2) cleaning reaction environment: after crucible is placed in microwave cavity, resonator cavity can be evacuated to 10～
50kPa, or it is passed through nitrogen or argon, in resonator cavity, form nitrogen or argon gas atmosphere, with cleaning or fall
The impact of low oxygen partial pressure；
3) Microwave Induced Plasma processes: opening microwave, regulation microwave power is 2～6kW, by raw material
Within the several seconds, even transient heating is to 1100～1250 DEG C, in the plasma that microwave and induction thereof produce,
Excite activation synthetic reaction 10～60 seconds.
4) product is collected: after the Microwave Induced Plasmas of 10～60 seconds process, i.e. obtain C/SiC
Coaxial fiber；Product can directly be collected, it is not necessary to the post processings such as purification.
For the type of carbon fiber, substantially form identical due to it, the response nothing to Microwave Induced Plasma
Significant difference, therefore the type of carbon fiber is unrestricted.According to the requirement of application, step 1) in institute
The carbon fiber stated is polyacrylonitrile (PAN) base carbon fibre, viscose-based carbon fiber, asphalt base carbon fiber or phenolic aldehyde
Resin-based carbon fiber.Prepare the coaxial fiber of C/SiC it is crucial that the top layer carbon atom of carbon fiber and silicon monoxide
Reaction in-situ, silica flour, silicon dioxide powder etc. be only produce silicon monoxide intermediate silicon source, the most right
The type of silica flour, silicon dioxide powder etc. is also unrestricted, the silica flour of the most various granularities, purity etc., silicon dioxide
Powder, is all applied to the present invention.
Step 3) in parameter explanation is set: controlling operating power is 2～6kW；Too low irradiation power,
Being not enough to induction and produce plasma, speed is accelerated in unstable state and activation degree is limited.But it is too high
Operating power, will cause energy exchange excessively violent, produce plasma ablation.Control process the time 10～
60 seconds.The too short process time, the SiC of formation is the most abundant, it is impossible to ensure to form continuous whole SiC
Protection shell.In the long response time, by excessive for the SiC containment vessel layer thickness making top layer, reduce carbon fiber
The diameter of core body, affects the combination property of the coaxial fiber of C/SiC.
Second technical problem to be solved by this invention, it is provided that a kind of quick based on Microwave Induced Plasma
Antioxidant effect prepared by the method for the coaxial fiber of acquisition carbon/carborundum (C/SiC) is good, initial oxidation temperature is high,
The coaxial fiber of carbon/carborundum that residual rate after high temperature continued oxidation is high.
For solving second technical problem, the technical solution adopted in the present invention is: a kind of carbon/carborundum is coaxial
Fiber: with carbon fiber as core body, one layer of carborundum protective layer of the covering of carbon fiber surface continuous uniform, carbonization
Silicon protective layer and densification zero defect when being combined in amplification 100,000 times of carbon fiber core；Described carborundum protection
Layer thickness is 50～600nm.
Know-why: the processing modes such as difference and traditional conduction, convection current, microwave radiation penetrates in realization
While formula body heat phase, also can produce electromagnetic field, anti-to the chemistry with atomic nucleus outer-shell electron pairing bonding
Response path even should can be changed by producing special coupling intervention effect.And lure at the irradiation of High-Power Microwave
Lead down, low temperature plasma can be formed on surface, not only can realize the intensification of moment, and material top layer
Atom also will be activated.Under the microwave radiation of more power, can also result in air ionization, or the surface of solids
The distillation of atom, strong plasma sparking even may result in plasma ablation.
The basic composition of carbon fiber is carbon, and it is excellent that the class graphite microcrystalline structure that its random layer stack is amassed makes carbon fiber have
Different electromagnetic property, has good response to microwave electromagnetic field.The present invention according to carbon fiber and microwave field it
Between quick features of response, based on High-Power Microwave electromagnetic field induction produce plasma heating reaction system,
Formed silicon source by silica flour and silicon dioxide powder, by redox reaction, quickly produce and silicon monoxide is provided
(SiO)；And by the carbon atom on the plasma exciatiaon activated carbon fiber top layer of microwave induced generation, with SiO
Reaction in-situ forms carborundum (SiC) protection shell, thus acquires the coaxial fiber of C/SiC.Due to microwave
Induced plasma processing procedure exists violent energy exchange, and excites activation process, astable
Processing procedure will break through the restriction of molecular balance, is conducive to acquiring C/SiC within the extremely short time coaxial
Fiber.
It is pointed out that for the electromagnetic techniques such as microwave, for preventing the most dry of each wave band electromagnetic wave
Disturb, particularly prevent the microwave interference to radio communication, broadcast, radar etc., clear stipulaties the most
Can be as heating or dry, the frequency range being applied to the application such as industry, scientific research and medical science only has four sections, i.e. distinguishes
For: L section, frequency is 890～940MHz, and centre wavelength is 0.330m；S section, frequency is 2.40～2.50GHz,
Centre wavelength is 0.122m；C section, frequency is 5.725～5.875GMHz, and centre wavelength is 0.052m；K
Section, frequency is 22.0～22.25GHz, and centre wavelength is 0.008m.I.e. mid frequency lays respectively at 433MHz,
915MHz, 2.45GHz, 28GHz.The present invention uses the magnetron commonly used as microwave source,
Process under current 2.45GHz center bin.
According to the operation principle of electromagnetic wave Yu electromagnetic field, with the other kinds of microwave source such as klystron, travelling-wave tube,
Also the superposition that can produce electromagnetic field in other frequency ranges collects, thus induces generation plasma.Therefore, this
Bright may extend to based on Microwave Induced Plasma process ultimate principle, use klystron, travelling-wave tube etc. its
The microwave source of his type, or mid frequency is positioned at the place of its all band such as 433MHz, 915MHz, 28GHz
Reason, the most quickly acquires the coaxial fiber of C/SiC, and therefore similar with present invention operation also should belong to
The related content of the present invention.
Beneficial effects of the present invention:
1) process is simply, easily operate.Non-environmental-pollution in preparation process, technique environmental protection, in preparation process
Except power consumption, do not produce waste gas, waste liquid, waste residue etc.；
2) cost of material is low, strong adaptability.Various carbon fibers all can be processed also by Microwave Induced Plasma
Generate the C/SiC composite fibre of coaxial configuration；The industrial goods such as commercially available silica flour, silicon dioxide are utilized to make
For silicon source, carry out the preparation of the coaxial fiber of C/SiC, and without raw material is carried out early stage pretreatment；
3) speed preparing the coaxial fiber of carbon/carborundum (C/SiC) is fast, and efficiency is high, Microwave Induced Plasma
Processing procedure, only need 10～60 seconds；
4) the coaxial fiber of C/SiC acquired, structure is preferable.Carborundum (SiC) protection that surface is formed
Layer continuous uniform, with the combination densification zero defect of carbon fiber core；
5) vacuum level requirements is low, can be in the coarse vacuum of 10～50kPa, or the normal pressure of nitrogen/argon gas shielded
Condition processes, and utilizes common mechanical pump or water ring pump just can reduce the impact of oxidizing atmosphere in furnace chamber；
Detection and the control of reaction compartment condition is carried out also without accurate vacuum meter etc.；
6) product form size is controlled, by adjusting carbon source and the mol ratio in silicon source in raw material, microwave induced
The process power of plasma, and the technological parameter such as process time, i.e. can get SiC containment vessel layer thickness
The coaxial fiber of different C/SiC；
7) the coaxial fiber of the carbon/carborundum (C/SiC) acquired, has the antioxidant effect of excellence, initial
Oxidizing temperature improves to more than 760 DEG C, and this oxidation can be attributed to the oxidation of surface carborundum；1100～
Residual rate after 1420 DEG C of high temperature above continued oxidation can reach more than 40%.
Accompanying drawing explanation
Fig. 1 is that Kim etc. synthesizes the stripping on the coaxial fiber surface of C/SiC obtained now based on VS mechanism
As；
Fig. 2 is C/SiC coaxial fiber surface SiC protection shell and the carbon fiber core of the synthesis such as Kim
Combination interface pattern；
Fig. 3 is the coaxial fiber (diametric plane) of carbon/carborundum (C/SiC)；
Fig. 4 is the coaxial fiber (axially) of carbon/carborundum (C/SiC)；
Fig. 5 is the C/SiO utilizing electrospinning process to obtain2Coaxial fiber；
Fig. 6 is compound use radio frequency directly-heated method and chemical gaseous phase depositing process prepares the coaxial fiber of C/SiC；
Fig. 7 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (3kW/55 second) obtained；
Fig. 8 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (3.0kW/20 second) obtained；
Fig. 9 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (2.0kW/30 second) obtained；
Figure 10 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (4.0kW/15 second) obtained；
Figure 11 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (5.5kW/10 second) obtained；
Figure 12 is that Microwave Induced Plasma processes the coaxial fiber of C/SiC (3.5kW/40 second) obtained.
Detailed description of the invention
Specific embodiments of the present invention are described below in detail.
Comparative example 1
Conventional chemical vapor sedimentation is used to prepare SiC coating
At present, the example using chemical vapour deposition technique to be prepared SiC coating has a lot.Such as document " CVD
Method prepares SiC advanced ceramics material progress " (material engineering, 2002 (7): 46-48) relate to a kind of use
Methyl trichlorosilane (MTS) is precursor, at 900～1600 DEG C, pyrolysis, the SiC of generation occurs
Gas is deposited on matrix surface by cooling solidification, forms SiC coating.Although the SiC prepared by the method
Purity is high, deposition temperature range width, but can release substantial amounts of HCl gas when MTS decomposes, and HCl gas is not
Only there is toxicity, and equipment is had stronger corrosivity, inadequate environmental protection.For another example document is " with liquid carbon
Silane is that precursor is for CVD SiC coating " in (material science and technique, 2007,15 (6): 848-850) also
Employ CVD, it is characterised in that with clean monocrystalline silicon piece and graphite flake as base substrate, use liquid carbon silicon
Alkane pioneers body, H2For carrier gas and protective gas, the mode of bubbling is used to bring precursor into deposition reaction
In room, continue evacuation to keep the low pressure of about 1kPa.Control depositing temperature between 800～900 DEG C, one
Lower the temperature after the section time, monocrystalline silicon piece obtains SiC coating.Although the coating that the method is prepared more light
Clean, SiC purity is the highest, and sedimentation rate can reach 40nm/min (2.4 μm/hr), but deposition coating layer thickness is not
Uniformly, the requirement to process equipment and experiment condition is higher, and course of reaction cannot be easily managed, and cost is the most relatively
High.
Analysis to chemical vapour deposition technique can find, this method prepares the special equipment that SiC coating needs are used
Complex, and it also requires use hydrogen as protective gas in a large number, it is long that course of reaction expends the time,
The cost of raw material is high, and the requirement to process equipment and experiment condition is higher, and course of reaction is difficult to obtain control
System, relatively common carrying out SiC for block or flaky matrix, but the such spy of fiber coaxial for C/SiC
Fixed structure, then has obvious difficulty in terms of preparation.
Comparative example 2:
Sol-gel process (Sol-Gel) is used to prepare the coaxial fiber of C/SiC.
At present, the example using sol-gel process to prepare SiC coating also has a lot.Such as document " Carbon fibe table
Face SiC/SiO2Prepared by the sol-gal process of ORC " (novel charcoal material, 2013,28 (3): 208-214)
Described in, at room temperature mix homogeneously with ethanol, MTES (MTES) with hydrochloric acid solution,
The collosol and gel precursor of stable transparent is obtained after airtight stirring 2h.Again by impregnated carbon fiber in sol solution
Dried, 1500 DEG C of heat treatment 2h under high-purity argon gas is protected, uniform in carbon fiber surface synthesis
SiC/SiO2Coating.
But the defect utilizing sol-gel process is more obvious, and particularly precursor preparation technology is complex,
Course of reaction consuming time length is the drawback that this method is intrinsic；And containing corrosive elements, synthesis in reactant
During there is substantial amounts of volatile contaminant, inadequate environmental protection so as to get product also need further to carry
Sublimate processes.
Comparative example 3
With the contrast using solid sintering technology to prepare SiC coating in carbon fiber surface
Solid sintering technology is to be applied to one of method preparing SiC coating very early.If Kim etc. is based on solid and gas
(VS) mechanism, takes, with Gu Te, 7 μm that Univ Cambridge Tech (Goodfellow Cambridge Limited) provides
Diameter carbon fibers, and the mixture of silicon dioxide powder, silica flour is presoma, is 80/20 by flow-rate ratio
Argon/hydrogen (Ar/H2) mixed flow gas protection under, in 1350～1400 DEG C react 5h, i.e. obtain
The coaxial fiber of C/SiC.Fiber coaxial to gained C/SiC carries out thermal oxide contrast in air, it is possible to find do not protect
The carbon fiber protected is relatively stable below 500 DEG C, 600 DEG C of dangerous cinders that i.e. burn.The oxygen of the coaxial fiber of C/SiC
Changing initial temperature to improve to 600 DEG C, 700～800 DEG C of ability rapid oxidation are weightless, but 700 DEG C of continuous oxidation 2h
Then carbon fiber core aoxidizes totally.Fig. 1 amplifies the photo of 5,000 times and shows, the surface SiC of formation manages not
Completely, the protection to carbon fiber core is difficult to completely；Fig. 2 pattern also indicates that, the inner surface of SiC pipe and carbon
The combination of fiber core is the most not ideal enough.[information contrast source: J W, Lee S S, Jung Y G, et al.
Synthesis of SiC microtube with villus-like morphology and SiC fiber[J].Journal of
Materials Reseauch,2005,20(2):409-416Kim】
And for example in patent CN 101003942 " a kind of method preparing coat of silicon carbide at carbon fiber surface "
Described, silica flour and carbon dust are mixed, loads in vacuum sphere grinding jar and grind to form mixed powder, be prepared as slurry；
Again carbon fiber is put in slurry, be dried after mix homogeneously, sinter, surface must be arrived there is SiC coating
Carbon fiber.
Although simple with solid sintering technology equipment when carbon fiber surface prepares SiC coating, but to experiment condition
Requirement harsh, building-up process needs circulation be passed through Ar/H2Protective atmosphere in, otherwise so long
In the high-temperature sintering process of time, carbon fiber is easy to be burnt, and also results in the raising of cost simultaneously.
Comparative example 4
With the contrast using precursor infiltration and pyrolysis method (PIP) to prepare carbon fiber surface SiC ORC
SiC coating is prepared as cracking process using the Polycarbosilane (PCS) of average molecular mass about 1500
Precursor, using dimethylbenzene as solvent.By PCS grind into powder, it is dissolved in dimethylbenzene, ultrasonic disperse system
For obtaining the PCS/ xylene solution that PCS mass fraction is 5～15%.Respectively by carbon fiber in a vacuum
Under conditions of being 1MPa with pressure, impregnate 1h with PCS/ xylene solution；Then dry at 100 DEG C
Dry, then crack in 950 DEG C to form SiC coating in the tube type resistance furnace of inert atmosphere protection.Circulation weight
Aforesaid operations is repeatedly again, to obtain the coaxial fiber of C/SiC.To carbon fiber and the C/SiC utilizing PIP method to obtain
Coaxial fiber carries out antioxygenic property and compares and can find, unprotected carbon fiber i.e. starts weightlessness at 400 DEG C,
550 DEG C of oxidations are completely.And the coaxial fiber of C/SiC containing SiC coating, oxidation initial temperature improves extremely
About 600 DEG C, the residual mass mark after 950 DEG C of heat treatments is still about 30%.[information contrast source: Xiao
The Chinese is peaceful, the impact on carbon fiber non-oxidizability of Chen Gangjun, Gao Pengzhao, Wang Chao, the SiC preparation technology of coating, Hunan
College journal, 2007,34 (8), 41-44]
And for example in patent CN 103266470 A " a kind of carbon fiber ORC and preparation method thereof ", will
Polycarbosilane (PCS) and tetraethyl orthosilicate add stirring and dissolving in dimethylbenzene and prepare precursor solution, then pressure leaching
Stain with the prefabricated carbon fiber body of pyrocarbon coating, in atmosphere in 160～220 DEG C time solidify 1～2h, then
In vacuum environment, at a temperature of 1000～1300 DEG C, crack 1～2h to prepare at carbon fiber surface
SiO2The SiC coating of doping.
But the raw material Polycarbosilane involved by the method is expensive, and organic solvent dimethylbenzene also has play
Toxicity, considerably increases preparation cost and danger.The cycle of the most whole building-up process is longer, relates to
The operations such as raw material dipping, solidification, Pintsch process so that combined coefficient reduces.Additionally, due in high-temperature hot
In cracking process, the degraded of organic resin and the volatilization of little molecule escape, although can be by repeated multiple times circulation
Dipping and pyrolysis processing, but still be difficult to eliminate the defects such as hole.And gained SiC coating is by repeatedly intermittent
Operation complete, at coutinuity of coating, all Shortcomings such as uniformity, at high temperature easily lead to boundary
Face separates, and antioxygenic property deterioration was even lost efficacy.
Comparative example 5
Contrast with the method using generating silicon carbide coating by using silicon thermal evaporation method
Thermal evaporation silicon process synthesis SiC coating is the most relatively common.Such as patent CN 102477694 A " thermal evaporation silicon
Method generates the method for coat of silicon carbide " in, silica flour or silico briquette fragment are put into bottom graphite crucible, fine with carbon
Dimension is horizontally placed on crucible top as carbon source, and is inverted an equal amount of crucible thereon to fix carbon fiber.
This device is put in high-temperature vacuum sintering furnace, is evacuated to 1～5Pa, under the protection of argon, be warming up to silicon
Fusing point more than, insulation 1～9h after cool down, i.e. generate one layer of coat of silicon carbide at carbon fiber surface.
Compared with traditional method, although to have equipment simple, without chlorosilane or Polycarbosilane pioneer for the method
Bromhidrosis body and hydrogen, it is not necessary to carry out the pretreatment of raw material, the advantage such as the products pure obtained, but during preparation
Between longer, at least need more than 1h.The a large amount of use of protective gas argon also result in cost raising simultaneously.
Comparative example 6
The thermal chemical vapor infiltrations such as compound use and pyrocarbon thermal response prepare the coaxial fiber of C/SiC
First by chopped fiber that polypropylene-base (PAN) carbon fiber chopped is length 3～5mm.Then the heat such as utilization
Chemical vapour infiltration (ICVI) technology, with methane as presoma, with nitrogen as diluent gas, at methane partial pressure
30kPa and the hot conditions of 1100 DEG C and lower continuous pyrolysis 1 hour, in carbon fiber surface deposition cladding
The pyrolytic carbon (PyC) that 200nm is thick.The most again in vacuum sintering furnace, graphite crucible holds titanium dioxide
Silica flour (SiO2) and silica flour (Si), and the mixture of chopped carbon fiber is (by SiO2It is placed on graphite with Si powder
Crucible bottom), under 1400～1600 DEG C of high temperature and 20Pa vacuum condition, successive reaction 1 hour, i.e. divides
Tong Guo silicon dioxide powder (SiO2) and silica flour (Si) reaction be initially formed and discharge silicon monoxide (SiO) gas, then
Continue reaction with the pyrolytic carbon (PyC) of carbon fiber surface and obtain carborundum (SiC) containment vessel, thus obtain
To the coaxial fiber of C/SiC.
Fig. 3 illustrates in " diametric plane " of the coaxial fiber of carbon/carborundum (C/SiC) visible, the SiC of fiber sheath
Protection shell is about 160nm, can between pyrolytic carbon (PyC) and carbon fiber core and carborundum protective layer
See more significantly interface.The showing of " axially " of the coaxial fiber of carbon/carborundum (C/SiC) is illustrated by Fig. 4
Micromorphology is it has been also found that due to the difference of thermal coefficient of expansion etc., on the protective layer of the coaxial fiber of gained C/SiC
There is obvious crackle.[information contrast source: Hejun Li, Haibo Ouyang, LehuaQi, Yulei Zhang,
Zhengjia Li and Jianfeng Wei.Effect of Temperature on the Synthesis of SiC
Coating on Carbon Fibers by the Reaction of SiO with the Deposited Pyrolytic
Carbon Layer, J.Mater.Sci.Technol., 2010,26 (3), 211-216.]
Contrast 7
C/SiO prepared by method of electrostatic spinning2Coaxial composite fibre
First by tetraethyl orthosilicate (TEOS), water, hydrochloric acid (HCl) according to mol ratio 1:2:0.01 mix homogeneously,
Join strong agitation 2h in ethanol in proper amount solvent, when Tyndall phenomenon occurs in colloidal sol, colloidal sol is placed in baking
60 DEG C of insulations in case, to promote that TEOS hydrolysis and ethanol are volatilized.To SiO2Dissolved adhesiveness increases to
Take out during 100mPa s.The another spinning nozzle transforming electrostatic spinning, makes coaxial double spinning nozzle by it.Then with
SiO2Colloidal sol is shell, and polyacrylonitrile (PAN) solution is sandwich layer, adopts under the driving voltage of 15～18kV
It is prepared for PAN/SiO by coaxial electrostatic spinning method2Coaxial fiber.To gained PAN/SiO2Coaxial fiber is carried out
Follow-up pre-oxidation, carbonization etc. process, and i.e. can get C/SiO2Coaxial fiber.[information contrast source: grandson
Good Kui, Cheng Haifeng, Chu Zengyong, Zhou Yongjiang, Sun Guoliang, C/SiO2Preparation and the performance of coaxial composite fibre are ground
Study carefully, Journal of Inorganic Materials, 2009,24 (2), 310-314]
But the modified effect of this carbon-fiber high-temperature antioxygenic property, hence it is evident that not as SiC protects shell.Fig. 5 is
Utilize the C/SiO that electrospinning process obtains2Coaxial fiber.Pattern shows, coaxial fibre diameter is about 1 μm,
Carbon fiber has the SiO of thickness about 20nm2Coating.
Comparative example 8
Compound use radio frequency directly-heated method and chemical gaseous phase depositing process prepare the coaxial fiber of C/SiC
Using carbon fiber as coated matrix, carbon fiber is positioned in RF-coupled chamber, occurs utilizing radio frequency
Under the radio-frequency electromagnetic field action that device produces, carbon fiber is internal produces faradic current, owing to carbon fiber has necessarily
Resistance and absorb radio-frequency (RF) energy and formed ohm heat.When belt current intensity is sufficiently large, carbon fiber body temperature
Can be increased to deposit required temperature.Chemical gaseous phase is used to deposit (CVD) method, with methyl trichlorosilane again
(CH3SiCl3) it is precursor raw material, with hydrogen (H2) it is carrier gas, argon (Ar) is dilution and protective gas,
Under the depositing temperature of 700～780 DEG C, coat one layer of SiC protective layer in carbon fiber surface low temperature.Fig. 6 is
Wang Cheng states of Shandong University etc. use radio frequency directly-heated method and chemical gaseous phase depositing process to prepare the coaxial fiber of C/SiC
Pattern.Photo shows, the coaxial fiber of C/SiC that the method obtains, and is limited by the relatively low grade of depositing temperature,
The SiC protective layer arrived is coarse, and fine and close not continuously, distribution and thickness etc. are the most uniform.[information
Contrast source: well is quick, Wang Chengguo, Zhu Bo, white jade is pretty, Wang Yanxiang, Chen Xinmou, and radio frequency directly-heated method is fine at carbon
Dimension surface low-temperature SiC Coating research, material engineering, 2005, (8), 53-58]；And for example patent CN
In 1461821A " technique of carbon fiber surface coating silicon carbide and device ", by radio frequency method fields focus
Device, is heated to 1100～1300 DEG C to the graphitized carbon fibre in motion, manufactures a chlorine while heating
Silane adds the reaction environment of high-purity hydrogen, and chlorosilane cracks, it is achieved that SiC is deposited on carbon fiber surface and is formed
Coating.
But radio frequency method prepares the device of SiC and technique is the most complex, the speed of wire, reaction temperature and
The controllability being filled with amount of reactant gases is the highest, directly affects the thickness of coating.Can produce during simultaneous reactions
Pollution gas, the product obtained is the purest.
Application example 1
With T300 type polypropylene (PAN) base carbon fibre, and silicon dioxide (SiO2) and silica flour (Si) be raw material.Will
Carbon/element silicon mol ratio C:Si=2:1 is pressed in carbon fiber and silicon source, mol ratio Si of silicon/silicon dioxide in silicon source:
SiO2The ratio dispensing of=1:1, mixing is placed in the resonator cavity of microwave oven.First it is evacuated to 15kPa left
The right side, then applies the microwave of 3kW.The excellent conductive characteristic of carbon fiber and realizing is utilized quickly to absorb micro-
Wave energy, by unique body phase self-heating, moment is warming up to about 1100 DEG C.Meanwhile, microwave induced
The plasma produced will excite and the carbon atom on activated carbon fiber surface.Silicon dioxide (SiO2) and silica flour (Si)
At high temperature react gaseous state silicon monoxide (SiO) intermediate of formation, the carbon atom activated with carbon fiber surface,
Carborundum (SiC) is generated by reaction in-situ.Through the continuous irradiation of 55 seconds, i.e. obtain thickness and be about
The SiC protective layer of 565nm.
With air as oxidizing atmosphere, fiber coaxial to PAN base carbon fibre and C/SiC carries out dynamic high temperature respectively
Oxidation test comparison.Result shows, the initial oxidation temperature of PAN base carbon fibre is about 410 DEG C, 625～
I.e. rapid weight loss, more than 823 DEG C thermal oxide noresidues between 788 DEG C.And the coaxial fiber of C/SiC rise
Beginning oxidizing temperature then improves to 790 DEG C, and ironically, owing to carborundum is to the conversion of silicon oxide, just
Not presenting weightlessness during the beginning, and be as persistently thickening of silica glass phase protecting film, coaxial fiber is slightly
Weightening finish；The temperature range that in the coaxial fiber of C/SiC, carbon fiber core substantially aoxidizes is delayed to 825～980 DEG C.
After more than 1100～1460 DEG C continue thermal oxide, the residual rate of coaxial fiber is still up to 46%.
Fig. 7 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma processes 55 seconds.Amplify 100,000
Times photo in visible, carbon fiber surface has been coated with the SiC protective layer of continuous uniform.Utilize with comparative example
The coaxial fiber of C/SiC that the various methods such as PIP method, CVD obtain is compared, and the present invention is with microwave induced etc.
It is substantially a continuous whole overall structure that gas ions processes the SiC protection shell obtained, surface without hole or
The defects such as crackle, and fine and close with the combination of carbon fiber core.
Application example 2
By asphalt base carbon fiber and silicon dioxide (SiO2) and silica flour (Si) be raw material.Carbon fiber and silicon source are pressed carbon/
Element silicon mol ratio C:Si=5:1, mol ratio Si:SiO of silicon/silicon dioxide in silicon source2The ratio of=2:1
Dispensing, mixing is placed in the resonator cavity of microwave oven.First in resonator cavity, it is passed through nitrogen (N2) as protection gas
Atmosphere, then applies the microwave of 3kW, and sample is brought rapidly up to about 1173 DEG C.Through the continuous spoke of 20 seconds
According to, i.e. obtain the SiC protective layer that thickness is about 260nm.
The high-temperature thermal oxidation characteristic of fiber coaxial to C/SiC carries out test display, and initial oxidation temperature is about
771 DEG C, and slightly increase weight；The fiber thermal weight loss of 805～940 DEG C of scopes is the most obvious；1100～1493 DEG C
After more than continuing thermal oxide, the residual rate of coaxial fiber is about 43%.
Fig. 8 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma 3.0kW processes 20 seconds.Amplify
The pattern of 100000 times shows, carbon fiber surface has been coated with the SiC protective layer of continuous uniform, and SiC shell with
The combination of carbon fiber core is fine and close.Compared with implementing, with comparative example, the coaxial fiber of C/SiC that additive method obtains,
The present invention processes with Microwave Induced Plasma and obtains SiC containment vessel continuous uniform surface without hole or crackle
Etc. defect and fine and close with the combination of carbon fiber core, it is combined into good overall structure with carbon fiber core layer,
Application example 3
With viscose-based carbon fiber and silicon dioxide (SiO2) and silica flour (Si) be raw material.Carbon fiber and silicon source are pressed carbon
/ element silicon mol ratio C:Si=3:1, mol ratio Si:SiO of silicon/silicon dioxide in silicon source2The ratio of=0.5:1 is joined
Material, mixing is placed in the resonator cavity of microwave oven.It is passed through argon (Ar) as protective atmosphere, then applies
The microwave exposure of 2.0kW, sample is brought rapidly up to about 1130 DEG C.Through the microwaves of 30 seconds and induction etc.
The continuous processing of gas ions, i.e. obtains the coaxial fiber of C/SiC.
The high-temperature thermal oxidation characteristic of fiber coaxial to C/SiC carries out test display, and initial oxidation temperature is about
762 DEG C, and slightly increase weight；800～928 DEG C of interval thermal weight losses are rapider；More than 1105～1420 DEG C
After continuing thermal oxide, the residual rate of coaxial fiber is about 41%.
Fig. 9 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma 2.0kW processes 30 seconds.Put
The pattern of big 100,000 times shows, carbon fiber surface has been coated with the SiC protective layer of continuous uniform, and thickness is about
51nm.With the C/SiC coaxial fiber phase utilizing the various methods such as PIP method, CVD to obtain in comparative example
Ratio, the present invention processes the SiC obtained and protects shell with Microwave Induced Plasma, and structural integrity is uniform, table
Face is without the defect such as hole or crackle and fine and close with the combination of carbon fiber core, is formed preferably with carbon fiber
Interface cohesion.
Application example 4
With T700 type polypropylene-base carbon fiber (PAN-CF) and silica flour (Si) and silicon dioxide powder (SiO2) it is former
Material.Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=4:1, in silicon source silicon/silicon dioxide mole
Compare Si:SiO2The ratio dispensing of=1.5:1, is positioned in the resonator cavity of microwave oven after mixing.First it is evacuated to
About 35kPa, then applies the microwave of 4.0kW, and sample is brought rapidly up to about 1220 DEG C.Through 15
The continuous irradiation of second, i.e. obtains the coaxial fiber of C/SiC.
The high-temperature thermal oxidation characteristic of fiber coaxial to C/SiC carries out test display, and initial oxidation temperature is about
806 DEG C, and slightly increase weight；The fiber thermal weight loss of 817～953 DEG C of scopes is relatively fast, to carbon fiber core
Protected effect good.The high temperature of more than 1117～1439 DEG C continues thermal oxide, the residual rate of coaxial fiber
Still about 47%.
Figure 10 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma 4.0kW processes 15 seconds.Put
The pattern of big 100,000 times shows, carbon fiber surface has been coated with the SiC protective layer of continuous uniform, and thickness is about
265nm.With the C/SiC coaxial fiber phase utilizing the additive methods such as PIP method, CVD to obtain in comparative example
Ratio, utilizes Microwave Induced Plasma to process the SiC protection shell and carbon fiber core obtained in the present invention
In conjunction with fine and close, interface zero defect, define the overall structure that morphosis is ideal.
Embodiment 5
With gas-phase growth of carbon fibre and silica flour (Si) and silicon dioxide powder (SiO2) it is raw material.By carbon fiber and silicon source
By carbon/element silicon mol ratio C:Si=5:1, mol ratio Si:SiO of silicon/silicon dioxide in silicon source2The ratio of=2:1
Dispensing, is positioned in the resonator cavity of microwave oven after mixing.First it is evacuated to about 25KPa, then applies
The microwave of 5.5kW, sample is brought rapidly up to about 1245 DEG C.Through the continuous irradiation of 10 seconds, i.e. obtain
The coaxial fiber of C/SiC.
The high-temperature thermal oxidation characteristic of fiber coaxial to C/SiC carries out test display, and initial oxidation temperature is about
781℃；The fiber thermal weight loss change of 810～915 DEG C of scopes is relatively fast, but still has carbon fiber core
More significantly protected effect.The high temperature of more than 1105～1436 DEG C continues thermal oxide, to carbon fiber core
Protective capability deteriorated, the oxidation of carbon fiber is more serious, and the residual rate of coaxial fiber is about 42%.
Figure 11 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma 5.5kW processes 10 seconds.Put
The pattern of big 100,000 times shows, carbon fiber surface has been coated with the SiC protective layer of continuous uniform, and thickness is about
70.3nm.Compared with the coaxial fiber of C/SiC that additive method in comparative example obtains, the present invention is with microwave induced
The SiC protection shell that Cement Composite Treated by Plasma obtains is substantially a continuous whole overall structure, and surface is without hole
Or the defect such as crackle, and fine and close with the combination of carbon fiber core.
Embodiment 6
With T800 type polyacrylonitrile (PAN) base carbon fibre and silica flour (Si) and silicon dioxide powder (SiO2) it is raw material.
Carbon fiber and silicon source are pressed carbon/element silicon mol ratio C:Si=4:1, the mol ratio of silicon/silicon dioxide in silicon source
Si:SiO2The ratio dispensing of=1:1, is positioned in the resonator cavity of microwave oven after mixing.First it is evacuated to 30Pa
Left and right, then applies the microwave of 3.5kW, and sample is brought rapidly up to about 1190 DEG C.Through the company of 40 seconds
Continuous irradiation, i.e. obtains the coaxial fiber of C/SiC.
The high-temperature thermal oxidation characteristic of fiber coaxial to C/SiC carries out test display, and initial oxidation temperature improves extremely
It is 781 DEG C, and slightly increases weight；Rapid Thermal weightless temperature interval is delayed to 827～945 DEG C of scopes；1117～
The high temperature of more than 1435 DEG C continues thermal oxide, and the oxidation of carbon fiber is relative, and the residual rate of coaxial fiber is about
44%.
Figure 12 is the coaxial fiber of C/SiC obtained after Microwave Induced Plasma 3.5kW processes 40 seconds.Put
The pattern of big 100,000 times shows, carbon fiber surface has been coated with the SiC protective layer of continuous uniform, and thickness is about
131nm.Compared with the coaxial fiber of C/SiC that additive method in comparative example obtains, the present invention is with microwave induced
The SiC protection shell that Cement Composite Treated by Plasma obtains is more complete uniformly, without the defect such as hole or crackle in structure,
And it is ideal with the combination of carbon fiber core.
Claims (5)
1. a preparation method for the coaxial fiber of carbon/carborundum, the steps include: by carbon fiber, silica flour, two
Silica powder forms mixture after being sufficiently mixed, and is placed under vacuum or noble gas normal pressure protective condition；Profit
With microwave, mixture is heated, make carbon fiber surface activate and excite pyroreaction, obtaining carbon/carborundum coaxial
Fiber, described microwave heating frequency is 433MHz, 915MHz or 2.45GHz, heating power be 2～
6kW, the described pyroreaction time is 10～60 seconds, described pyroreaction temperature be 1100～
1250℃。
The preparation method of a kind of coaxial fiber of carbon/carborundum the most according to claim 1, its feature exists
In: carbon and element silicon mol ratio are 2～5:1, and described silica flour with the mol ratio of silicon dioxide is
0.5～2:1.
The preparation method of a kind of coaxial fiber of carbon/carborundum the most according to claim 1 and 2, it is special
Levy and be: described vacuum condition pressure is 10～50kPa；Described noble gas is argon or nitrogen.
The preparation method of a kind of coaxial fiber of carbon/carborundum the most according to claim 1 and 2, it is special
Levy and be: described carbon fiber be polyacrylonitrile-based carbon fibre, viscose-based carbon fiber, asphalt base carbon fiber or
Phenolic resin base carbon fibre.
5. prepared by the preparation method utilizing a kind of coaxial fiber of carbon/carborundum described in claim 1 or 2
The coaxial fiber of carbon/carborundum, it is characterised in that: the described coaxial fiber of carbon/carborundum with carbon fiber as core body,
One layer of carborundum protective layer of the covering of carbon fiber surface continuous uniform, carborundum protective layer and carbon fiber core
Densification zero defect when being combined in amplification 100,000 times；Carborundum protective layer thickness is 50～600nm.
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| CN105256407B (en) * | 2015-11-03 | 2017-08-08 | 西北工业大学 | The carbon silicon carbide compound nanofiber and preparation method of " nucleocapsid " structure based on coaxial electrostatic spinning technique |
| CN106784667B (en) * | 2016-12-12 | 2019-06-25 | 武汉科技大学 | A kind of charcoal material surface SiC Nanometer Whiskers and preparation method thereof |
| CN108118524A (en) * | 2017-12-08 | 2018-06-05 | 北京科技大学 | A kind of preparation of coaxial configuration absorbing material and performance regulation and control method |
| FR3075829B1 (en) * | 2017-12-26 | 2020-09-04 | Safran Ceram | METHOD AND DEVICE FOR DEPOSITING A COATING ON A CONTINUOUS FIBER |
| CN111087245A (en) * | 2020-01-17 | 2020-05-01 | 泰州市海创新能源研究院有限公司 | Method for synthesizing low-oxygen low-carbon-content SiC fibers by gas phase method |
| CN113135768B (en) * | 2021-03-19 | 2022-06-03 | 西安理工大学 | Preparation method of hollow porous SiC fibers |
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